CN108134067A - Adulterate La in a kind of surface layer3+NCM tertiary cathode materials preparation method - Google Patents

Adulterate La in a kind of surface layer3+NCM tertiary cathode materials preparation method Download PDF

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CN108134067A
CN108134067A CN201711417975.4A CN201711417975A CN108134067A CN 108134067 A CN108134067 A CN 108134067A CN 201711417975 A CN201711417975 A CN 201711417975A CN 108134067 A CN108134067 A CN 108134067A
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tertiary cathode
ncm811
cathode materials
doping
ncm
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苏岳锋
李晴
吴锋
卢赟
陈来
包丽颖
陈实
王敬
张其雨
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Beijing Institute of Technology BIT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract

The present invention relates to a kind of surface layers to adulterate La3+NCM tertiary cathode materials preparation method, belong to field of chemical energy storage battery.The method of the invention is to carry out La during nickel cobalt manganese hydroxide precursor is mixed with lithium salts3+Doping, the La of doping3+It enters in the transition metal layer on surface layer, occupies Ni2+Position, can play braced frame, inhibit surface structure phase transformation and inhibit Li+/Ni2+The effect of mixing；In addition, La3+Ionic radius it is bigger, doping enter transition metal layer after, help to widen Li+It is embedded it is embedding go out channel, help to improve Li+Transmission rate, chemical property of the NCM tertiary cathode materials under high voltage high magnification (4.5V, >=1C) can be significantly improved.

Description

Adulterate La in a kind of surface layer3+NCM tertiary cathode materials preparation method
Technical field
The present invention relates to a kind of surface layers to adulterate La3+NCM tertiary cathode materials preparation method, belong to chemical energy storage battery Field.
Background technology
At present, the fossil energies increasingly depleted such as coal, oil, natural gas, in addition, problem of environmental pollution is increasingly becoming various countries pass The Important Problems of note.The development that pure electric automobile and oil and gas mix electrical automobile is more and more of interest by people.This just needs lithium secondary Battery fast development is to meet active demand of the people for new energy battery practical application.In the family of lithium secondary battery, cobalt Sour lithium, LiFePO4 and ternary material performer key player in the market successively.Cobalt acid lithium is applied to Miniature portable more Electronic equipment, and LiFePO4 just gradually replaces it in power electric automobile since specific discharge capacity is relatively low by ternary material The effect that aspect plays.After tesla's publication in 2012 using NCA (Li [Ni0.85Co0.1Al0.05]O2) tertiary cathode material conduct After the electric vehicle Model S of power battery, the tide of tertiary cathode material (including NCM and NCA) is studied not all over the world Disconnected raising.China is high to meet a new generation also in development high voltage, the nickelic anode ternary material (NCM, NCA) done one's utmost The requirement of capacity electrode material.
NCM(Li[NixCoyMn1-x-y]O2, x>0.5) tertiary cathode material have higher specific discharge capacity (>200mAh/g), It realizes and is mentioned in China " 13 " new-energy automobile emphasis special project, industrialization lithium ion battery is realized to the year two thousand twenty Energy density reaches more than 300Wh/Kg, cost is down to the most potential positive battery material of 0.8 yuan/below Wh.But at present NCM tertiary cathode materials obtain extensive commercial applications not yet, one of the main reasons for this be exactly its stable circulation performance and High rate performance is poor.This is because Ni elements can occur in NCM tertiary cathode material building-up processes segregation and surface richness Collection, and Li+And Ni2+Ionic radius it is close, then in charge discharge cyclic process, it is easy to Li occur+/Ni2+It is mixed Row, makes the structure of NCM tertiary cathode materials change, so as to influence the electrochemical stability of NCM tertiary cathode materials and electricity Chemical cycle performance (Nickel-Rich and Lithium-Rich Layered Oxide Cathodes:Progress and Perspectives, Arumugam Manthiram, James C.Knight, Seung-Taek Myung, Seung-Min Oh, and Yang-Kook Su,Adv.Energy Mater.2016,6,1501010)。
Since under de- lithium state, Ni ions are reduced to Ni4+Ion, and the Ni on NCM tertiary cathode materials surface layer4+Pole It is unstable；Meanwhile high pressure causes electrolyte that oxygenolysis easily occurs, decomposition product is deposited on NCM tertiary cathode materials surface, electricity Acidic materials in solution liquid are likely to further corrode NCM tertiary cathode materials surface layer.For these reasons, NCM tertiary cathodes Material surface can occur to be changed from layer structure to spinel structure.And the it is believed that phase transformation of NCM tertiary cathode materials Journey is gradually spread from the surface to the internal, so the stability for strengthening NCM tertiary cathode materials surface layer is particularly significant.By grinding Study carefully discovery, the doping of other metallic elements is carried out to NCM tertiary cathode materials can improve its chemical property, but at present also not It sees and La is carried out to NCM tertiary cathode materials3+The report of doping.
Invention content
For NCM tertiary cathode materials surface structure it is unstable in cyclic process the problem of, the purpose of the present invention exists La is adulterated in providing a kind of surface layer3+NCM tertiary cathode materials preparation method, this method is in NCM tertiary cathode materials Presoma carries out La during being mixed with lithium salts3+Doping, the La of doping3+It enters in the transition metal layer on surface layer, Occupy Ni2+Position, can play braced frame, inhibit surface structure phase transformation and inhibit Li+/Ni2+The effect of mixing, can Significantly improve chemical property of the NCM tertiary cathode materials under high voltage high magnification (4.5V, >=1C).
The purpose of the present invention is what is be achieved through the following technical solutions.
Adulterate La in a kind of surface layer3+NCM tertiary cathode materials preparation method, the doping La3+NCM tertiary cathodes The chemical formula of material is Li [Ni0.8-xCo0.1Mn0.1Lax]O2, wherein 0.005≤x≤0.03；
The method step is as follows,
By nickel cobalt manganese hydroxide precursor powder (Ni0.8Co0.1Mn0.1(OH)2), lanthanum nitrate powder and lithium hydroxide Powder after mixing, then is placed under oxygen atmosphere and is calcined；Wherein, 4h~6h is first kept the temperature at 450 DEG C~550 DEG C, then It is warming up to 750 DEG C~850 DEG C and keeps the temperature 12h~20h, furnace cooling obtains surface layer doping La3+NCM tertiary cathode materials, letter It is denoted as La-NCM811.
Wherein, the mole ratio of the molal quantity of lithium hydroxide and nickel cobalt manganese hydroxide precursor powder for 0.98~ 1.05:1, the molal quantity of lanthanum nitrate is 1 with the molar ratio of nickel ion in nickel cobalt manganese hydroxide precursor powder:(25.6~ 159)。
Further, first by lithium hydroxide add in mortar in, dry grind 10min~15min, by lithium hydroxide particulate abrasive into Powder contributes to Li+Uniformly mixed in nickel cobalt manganese Strong oxdiative object presoma, then with lanthanum nitrate powder and nickel cobalt manganese hydroxide Object presoma ultrasound 1h~2h, then the mixture after ultrasound is transferred in mortar in ethanol, first dry grind 20min~30min Afterwards, ethyl alcohol wet-milling 20min~30min is added, then is placed under oxygen atmosphere and is calcined.
Advantageous effect：
(1) the method for the invention is with lithium salts add in mixed process in nickel cobalt manganese hydroxide precursor powder La is realized in lanthanum source3+On surface layer, transition metal layer adulterates, the La of doping3+Occupy Ni2+Position, in Li+It is a large amount of it is embedding go out mistake Cheng Zhong, La3+It can play the role of rock-steady structure frame, but also surface structure can be inhibited to occur in electrochemistry cyclic process The phase transformation changed from layer structure to spinel structure, while inhibit Li+/Ni2+The effect of mixing retains more lithium positions, from And realize Li+Preferably it is embedding go out/invertibity that be embedded in, so improving NCM tertiary cathode materials in charge discharge cycle The structural stability and reversible discharge capacity of process.
(2) combination between La-O can be more than the combination energy between other M-O (M=Ni, Co or Mn), so being entrained in table The La of layer transition metal layer3+Help to stablize lattice structure, especially stablize lattice structure under high pressure, alleviate nickelic Material in height by oxygen release is serious under voltage the problem of, significantly improve NCM tertiary cathode materials high voltage high magnification (4.5V, >=1C) under chemical property；In addition, La3+Ionic radius it is bigger, doping enter transition metal layer after, help to open up Wide Li+It is embedded it is embedding go out channel, help to improve Li+Transmission rate, so as to which the electrochemistry for improving NCM tertiary cathode materials is followed Ring performance.
(3) the raw materials used in the present invention derives from a wealth of sources, cheap, and the method operating process is simple, technique and skill Art is easy to implement, can be with large-scale commercial application, while this method can be used for other tertiary cathode materials or rich lithium just The surface of pole material carries out La3+Doping.
Description of the drawings
X-ray diffraction (XRD) spectrogram of NCM811 that Fig. 1 is La-NCM811 prepared by embodiment 1 and prepared by comparative example 1 Comparison diagram.
Fig. 2 is the CR2025 button cells cycle 1 assembled using La-NCM811 prepared by embodiment 1 as positive electrode AC impedance (EIS) test charts all and that cycle is after 10 weeks.
Fig. 3 is the CR2025 button cells cycle 1 assembled using La-NCM811 prepared by embodiment 1 as positive electrode Cyclic voltammetric (CV) curve graphs all and that cycle is after 10 weeks.
Fig. 4 is to be recycled using La-NCM811 prepared by embodiment 1 as the CR2025 button cells that positive electrode assembles Before, cycle 1 week and recycle 10 weeks after X-ray diffractogram.
Fig. 5 be the CR2025 button cells cycle that is assembled using NCM811 prepared by comparative example 1 as positive electrode 1 week with Recycle the ac impedance measurement figure after 10 weeks.
Fig. 6 be the CR2025 button cells cycle that is assembled using NCM811 prepared by comparative example 1 as positive electrode 1 week with Recycle the cyclic voltammetry curve figure after 10 weeks.
Fig. 7 is before being recycled using NCM811 prepared by comparative example 1 as the CR2025 button cells that positive electrode assembles, followed The X-ray diffractogram of ring 1 week and cycle after 10 weeks.
Fig. 8 is the CR2025 button cells that embodiment 1 assembles and the CR2025 button cells that comparative example 1 assembles in 2.75V Cycle performance curve graph under~4.35V voltage ranges and 1C (1C=200mAh/g) multiplying power.
Fig. 9 is the CR2025 button cells that embodiment 1 assembles and the CR2025 button cells that comparative example 1 assembles in 2.75V Cycle performance curve graph under~4.5V voltage ranges and 1C (1C=200mAh/g) multiplying power.
Figure 10 is that the CR2025 button cells that embodiment 1 assembles and the CR2025 button cells that comparative example 1 assembles exist successively The high rate performance figure obtained for 5 weeks is recycled under the multiplying power of 0.1C, 0.2C, 1C, 2C, 5C, 10C respectively.
Figure 11 is that the CR2025 button cells of Examples 1 to 4 assembling and the CR2025 button cells of the assembling of comparative example 1 exist Cycle performance curve graph under 2.75V~4.5V voltage ranges and 0.1C multiplying powers.
Specific embodiment
To be best understood from the present invention, the present invention is described in further detail with reference to specific embodiment.It should be understood that , the specific embodiments described herein are merely to illustrate and explain the present invention, are not intended to restrict the invention.In addition, The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or value should manage It solves as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, each range It between endpoint value and individual point value and can be individually combined with each other between point value and obtain one or more new numerical value Range, these numberical ranges should be considered as specific open herein.
In following embodiment：
X-ray diffractometer：Instrument model is Rigaku Ultima IV, Japanese；
Ac impedance measurement：CHI604c electrochemical workstations, China；Test voltage is 4.5V, frequency range 0.01Hz ~0.1MHz, the amplitude of sine wave AC voltage disturbing signal are 5m, using to electrode as reference electrode；
Cyclic voltammetry：CHI660e electrochemical workstations, China；Test voltage section be 2V~4.8V, sweep speed 0.1mV/s；
The assembling and test of CR2025 button cells：By positive electrode (La-NCM811 or comparison prepared by Examples 1 to 6 NCM811 prepared by example 1), acetylene black, PVDF (Kynoar) is according to 8:1:1 mass ratio is made slurry and coated in aluminium foil On, the aluminium foil of the load slurry of drying is cut into the sequin that diameter is about 1cm with slitter and is used as anode, is made with metal lithium sheet For cathode, Celgard2300 be diaphragm, 1M carbonate solution be that (it is 1 that wherein, solvent is volume ratio to electrolyte:1 carbonic acid The mixed solution of vinyl acetate and dimethyl carbonate, solute LiPF6), CR2025 button cells are assembled into argon gas glove box； Constant current is carried out using CT2001AAlnd cell testers under different current densities to the CR2025 button cells assembled to fill Discharge test, it is 200mA/g to define 1C current densities, and charging/discharging voltage section is 2.75V~4.35V and 2.75V~4.5V, is surveyed It is 30 DEG C to try temperature；When high rate performance is tested, respectively under the different current density of 0.1C, 0.2C, 1C, 2C, 5C, 10C, 0.1C Each cycle 5 weeks, progress constant current charge-discharge test, wherein, after 2C, 5C, 10C high magnification constant-current charge, then constant-voltage charge 1 hour Or constant-voltage charge is less than 0.05C to current density.
Ni used in Examples 1 to 60.8Co0.1Mn0.1(OH)2It is to be prepared according to the method described in comparative example 1 It obtains.
Embodiment 1
First by LiOHH2O add in mortar in, dry grind 15min after, then with Ni0.8Co0.1Mn0.1(OH)2And La (NO3)3·6H2Mixture after ultrasound, is then transferred in mortar by O ultrasound 1.5h in ethanol, and first dry grind 25min, then adds Enter ethyl alcohol and continue to grind 25min, then the mixture after wet-milling is placed in oxygen atmosphere, be first heated to 450 DEG C and keeps the temperature 6h, It is warming up to 750 DEG C again and keeps the temperature 12h, furnace cooling obtains surface layer doping La3+NCM tertiary cathode materials Li [Ni0.79Co0.1Mn0.1La0.01]O2, it is abbreviated as La-NCM811；Wherein, LiOHH2O and Ni0.8Co0.1Mn0.1(OH)2Mole Than being 1.05:1, La (NO3)3·6H2O and Ni0.8Co0.1Mn0.1(OH)2The molar ratio of middle nickel ion is 1:79.
CR2025 button cells are assembled into using the La-NCM811 prepared by embodiment 1 as positive electrode, and are carried out corresponding Electrochemical property test.
From the XRD spectra in Fig. 1 it is found that the La-NCM811 prepared by the present embodiment is not changing original nickelic ternary just The main crystal structure of pole material NCM811, both typical α-NaFeO2Structure belongs to R-3m space groups.It is most lower in Fig. 1 The vertical line of side is PDF#09-0063, represents perfect layer structure LiNiO2Characteristic peak positions, illustrate surface layer adulterate La3+It is front and rear Nickelic ternary material NCM811 be all perfect layer structure.But from θ=18.5o~19.5oAnd θ=44o~45oAt two Partial enlargement XRD diagram in it is found that La-NCM811 (003) peak and (104) peak it is micro- with respect to NCM811 inclined to low angle It moves, illustrates La3+Into after the transition metal layer of surface layer, due to La3+Ionic radius (r=0.106nm) more than Ni2+Ion Radius (r=0.069nm), surface layer doping La3+The interlamellar spacing of positive electrode afterwards increases, this is beneficial to Li+Insertion and Abjection.La is adulterated by the surface layer listed in table 13+The variation of front and rear cell parameter is it is found that by La3+Structure cell after doping The value of parameter a and c all increase, and c/a values also increase, and illustrate doping La3+Layered cathode material crystallinity afterwards is more preferable； (003) peak of La-NCM811 and the ratio at (104) peak significantly increase, it was demonstrated that adulterate La in surface layer3+Help to inhibit Li+/Ni2+ Mixing.In addition, since the binding force between La-O keys is far longer than the binding force between other M-O (M=Ni, Co or Mn) keys, La2O3Gibbs free energy of formation (- 1706.2KJ/mol) more than MnO2With the Gibbs free energy of formation of NiO (- 465.1KJ/mol, -211.7KJ/mol), it is more conducive to stablize the variation of the O ions in electrochemistry cyclic process, inhibits in height Under pressure condition the problem of positive electrode oxygen release.
To being existed using the La-NCM811 prepared by the present embodiment as the CR2025 button cells that positive electrode assembles EIS tests are carried out respectively after being recycled 1 week and 10 weeks under 2.75V~4.5V voltage ranges and 0.1C multiplying powers, and test result is detailed See Fig. 2；To using the NCM811 prepared by comparative example 1 as the CR2025 button cells that positive electrode assembles 2.75V~ EIS tests are carried out respectively after being recycled 1 week and 10 weeks under 4.5V voltage ranges and 0.1C multiplying powers, and test result refers to Fig. 5.Figure The charge transfer resistance R of the arc representation positive electrode of low frequency range in 2 and Fig. 5ct, it can be seen that it is recycled by first week and 10 weeks Afterwards, the charge transfer resistance R of La-NCM811ctIt is significantly less than the R of NCM811ct, show that La is adulterated on surface layer3+Positive electrode in electricity In chemical looping process, surface layer lattice structure is more stable, the polarization smaller of formation.
To being existed using the La-NCM811 prepared by the present embodiment as the CR2025 button cells that positive electrode assembles CV tests are carried out respectively after being recycled 1 week and 10 weeks under 2.75V~4.5V voltage ranges and 0.1C multiplying powers, and test result refers to Fig. 3；To the CR2025 button cells that are assembled using the NCM811 prepared by comparative example 1 as positive electrode in 2.75V~4.5V CV tests are carried out respectively after being recycled 1 week and 10 weeks under voltage range and 0.1C multiplying powers, and test result refers to Fig. 6.According to fig. 3 Test result with Fig. 6 is it is found that after the first cycle of week and 10 weeks, there is no the position at peak nearly all in the CV of two kinds of positive electrodes Offset, but the peak intensity after NCM811 is recycled 10 weeks is significantly reduced than the peak intensity after cycle head weeks, and La-NCM811 cycles 10 Peak intensity after week is almost unchanged, illustrates that the capacity retention ratio of cycle NCM811 after 10 weeks is lower, that is, carries out redox tribute Offering the substance of capacity reduces.
Respectively to La-NCM811 after being recycled 1 week and 10 weeks under 2.75V~4.5V voltage ranges and 0.1C multiplying powers into Row XRD is tested, and the results are shown in Figure 4；Respectively to being recycled 1 week under 2.75V~4.5V voltage ranges and 0.1C multiplying powers and NCM811 carries out XRD tests after 10 weeks, and the results are shown in Figure 7, and the vertical line below wherein Fig. 4 and Fig. 7 is PDF#09-0063.Root According to the test result of Fig. 4 and Fig. 7 it is found that the layer structure of positive electrode still keeps fine after cycle, but according to 18.5 ° Partial enlarged view at~19.5 ° and 44 °~45 ° is it is found that there is offset, and NCM811 in the position at (003) peak and (104) peak The offset of peak position to high angle is more serious, illustrates that NCM811 is more aobvious as the carry out structural lattice of electrochemistry cyclic process reduces It writes, that is to say, that NCM811 is in embedding de- Li+During since lattice has occurred in structural instability the structure changes such as collapse so that The value of cell parameter c and a reduce, and La-NCM811 lattice variations in cyclic process are not notable, also turned out surface layer doping La3+In embedding de- Li+During inhibit the variation of positive electrode lattice structure, significantly improve structural stability, also It is the cycle performance for improving positive electrode.
Using the CR2025 button cells assembled using the La-NCM811 prepared by the present embodiment as positive electrode and adopt The CR2025 button cells assembled by the use of the NCM811 prepared by comparative example 1 as positive electrode, in 2.75V~4.35V voltage zones Between, 1C multiplying powers and 30 DEG C of progress constant current charge-discharge tests, test result refer to Fig. 8；In 2.75V~4.5V voltage ranges, 1C multiplying powers and 30 DEG C of progress constant current charge-discharge tests, test result refer to Fig. 9.According to the test result of Fig. 8 it is found that In 2.75V~4.35V voltage ranges, the first all discharge capacities of NCM811 cycles are 170.8mAh/g, and electric discharge of the cycle after 500 weeks is held It measures as 111.9mAh/g, capacity retention ratio 65.5%；The first all discharge capacities of La-NCM811 cycles are 171.7mAh/g, are recycled After 500 weeks discharge capacity be 119.1mAh/g, capacity retention ratio 69.4%, at this point, the cycle performance ratio of La-NCM811 The cycle performance of NCM811 is slightly good.According to the test result of Fig. 9 it is found that in 2.75V~4.5V voltage ranges, NCM811 first weeks Discharge capacity is 194mAh/g, and discharge capacity of the cycle after 500 weeks is 44.2mAh/g, capacity retention ratio 22.8%；La- The all discharge capacities of head of NCM811 are 193.9mAh/g, and discharge capacity of the cycle after 500 weeks is 98.1mAh/g, capacity retention ratio It is 50.6%, then under high blanking voltage state, La-NCM811 has a clear superiority in terms of the stability for maintaining material.
Using the CR2025 button cells assembled using the La-NCM811 prepared by the present embodiment as positive electrode and adopt The CR2025 button cells assembled by the use of the NCM811 prepared by comparative example 1 as positive electrode, in 2.75V~4.35V and It at 2.75V~4.5V voltage ranges and 30 DEG C, recycles 5 weeks, tests respectively in 0.1C, 0.2C, 1C, 2C, 5C and 10C successively The results detailed in Figure 10.According to the test result of Figure 10 it is found that in 2.75V~4.35V voltage ranges, NCM811 is under 10C multiplying powers Discharge capacity for 151.1mAh/g, discharge capacities of the La-NCM811 under 10C multiplying powers is 161.1mAh/g；2.75V~ 4.5V voltage ranges, discharge capacities of the NCM811 under 10C multiplying powers be 165.5mAh/g, La-NCM811 putting under 10C multiplying powers Capacitance is 172.2mAh/g, further illustrates that the structure of La-NCM811 is more stable, the electrochemistry under high voltage high magnification It can be more excellent.
To the CR2025 button cells assembled using the La-NCM811 prepared by the present embodiment as positive electrode and adopt The CR2025 button cells assembled by the use of the NCM811 prepared by comparative example 1 as positive electrode 2.75V~4.5V voltage ranges, Constant current charge-discharge test is carried out at 0.1C multiplying powers and 30 DEG C.According to the test result of Figure 11 it is found that NCM811 head Zhou Fang electricity Capacity is 206mAh/g, and discharge capacity decays to 182.3mAh/g, capacity retention ratio 88.5% after cycle 30 weeks；La- The first all discharge capacities of NCM811 are 209mAh/g, and discharge capacity decays to 196.4mAh/g after recycling 30 weeks, and capacity retention ratio is 94%.
Table 1
Embodiment 2
First by LiOHH2O add in mortar in, dry grind 15min after, then with Ni0.8Co0.1Mn0.1(OH)2And La (NO3)3·6H2Mixture after ultrasound, is then transferred in mortar, first dry grind 25min, adds by O ultrasound 2h in ethanol Ethyl alcohol simultaneously continues to grind 25min, then the mixture after wet-milling is placed in oxygen atmosphere, be first heated to 450 DEG C and keeps the temperature 6h, then It is warming up to 750 DEG C and keeps the temperature 12h, furnace cooling obtains surface layer doping La3+NCM tertiary cathode materials Li [Ni0.795Co0.1Mn0.1La0.005]O2, it is abbreviated as La-NCM811；Wherein, LiOHH2O and Ni0.8Co0.1Mn0.1(OH)2Rub You are than being 1.05:1, La (NO3)3·6H2O and Ni0.8Co0.1Mn0.1(OH)2The molar ratio of middle nickel ion is 1:159.
La-NCM811 prepared by embodiment 2 is assembled into CR2025 button cells as positive electrode and carries out electrochemistry Performance test.Constant current charge-discharge test, first Zhou Fang electricity are carried out under 2.75V~4.5V voltage ranges, 30 DEG C and 0.1C multiplying powers Capacity is 211.3mAh/g, and discharge capacity of the cycle after 30 weeks is 191.3mAh/g, capacity retention ratio 90.5%, such as Figure 11 institutes Show.Constant current charge-discharge test is carried out under 2.75V~4.5V voltage ranges, 30 DEG C and 1C multiplying powers, first week discharge capacity is 190.8mAh/g, discharge capacity of the cycle after 500 weeks is 99.8mAh/g, capacity retention ratio 52.3%.
Embodiment 3
First by LiOHH2O add in mortar in, dry grind 15min after, then with Ni0.8Co0.1Mn0.1(OH)2And La (NO3)3·6H2Mixture after ultrasound, is then transferred in mortar, first dry grind 25min, adds by O ultrasound 2h in ethanol Ethyl alcohol simultaneously continues to grind 25min, then the mixture after wet-milling is placed in oxygen atmosphere, be first heated to 450 DEG C and keeps the temperature 6h, then It is warming up to 750 DEG C and keeps the temperature 12h, furnace cooling obtains surface layer doping La3+NCM tertiary cathode materials Li [Ni0.785Co0.1Mn0.1La0.015]O2, it is abbreviated as La-NCM811；Wherein, LiOHH2O and Ni0.8Co0.1Mn0.1(OH)2Rub You are than being 1.05:1, La (NO3)3·6H2O and Ni0.8Co0.1Mn0.1(OH)2The molar ratio of middle nickel ion is 1:52.3.
La-NCM811 prepared by embodiment 3 is assembled into CR2025 button cells as positive electrode and carries out electrochemistry Performance test.Constant current charge-discharge test, first Zhou Fang electricity are carried out under 2.75V~4.5V voltage ranges, 30 DEG C and 0.1C multiplying powers Capacity is 206.3mAh/g, and discharge capacity of the cycle after 30 weeks is 187.4mAh/g, capacity retention ratio 90.8%, such as Figure 11 institutes Show.Constant current charge-discharge test is carried out under 2.75V~4.5V voltage ranges, 30 DEG C and 1C multiplying powers, first week discharge capacity is 192.4mAh/g, discharge capacity of the cycle after 500 weeks is 101.8mAh/g, capacity retention ratio 52.9%.
Embodiment 4
First by LiOHH2O add in mortar in, dry grind 15min after, then with Ni0.8Co0.1Mn0.1(OH)2And La (NO3)3·6H2Mixture after ultrasound, is then transferred in mortar, first dry grind 25min, adds by O ultrasound 2h in ethanol Ethyl alcohol simultaneously continues to grind 25min, then the mixture after wet-milling is placed in oxygen atmosphere, be first heated to 450 DEG C and keeps the temperature 6h, then It is warming up to 750 DEG C and keeps the temperature 12h, furnace cooling obtains surface layer doping La3+NCM tertiary cathode materials Li [Ni0.77Co0.1Mn0.1La0.03]O2, it is abbreviated as La-NCM811；Wherein, LiOHH2O and Ni0.8Co0.1Mn0.1(OH)2Mole Than being 1.05:1, La (NO3)3·6H2O and Ni0.8Co0.1Mn0.1(OH)2The molar ratio of middle nickel ion is 1:25.7.
La-NCM811 prepared by embodiment 4 is assembled into CR2025 button cells as positive electrode and carries out electrochemistry Performance test.Constant current charge-discharge test, first Zhou Fang electricity are carried out under 2.75V~4.5V voltage ranges, 30 DEG C and 0.1C multiplying powers Capacity is 206.4mAh/g, and discharge capacity of the cycle after 30 weeks is 188.9mAh/g, capacity retention ratio 91.5%, such as Figure 11 institutes Show.Constant current charge-discharge test is carried out under 2.75V~4.5V voltage ranges, 30 DEG C and 1C multiplying powers, first week discharge capacity is 188mAh/g, discharge capacity of the cycle after 500 weeks is 94.5mAh/g, capacity retention ratio 50.3%.
Embodiment 5
First by LiOHH2O add in mortar in, dry grind 10min after, then with Ni0.8Co0.1Mn0.1(OH)2And La (NO3)3·6H2Mixture after ultrasound, is then transferred in mortar by O ultrasound 1.5h in ethanol, and first dry grind 30min, then adds Enter ethyl alcohol and continue to grind 30min, then the mixture after wet-milling is placed in oxygen atmosphere, be first heated to 500 DEG C and keeps the temperature 5h, It is warming up to 800 DEG C again and keeps the temperature 15h, furnace cooling obtains surface layer doping La3+NCM tertiary cathode materials Li [Ni0.79Co0.1Mn0.1La0.01]O2, it is abbreviated as La-NCM811；Wherein, LiOHH2O and Ni0.8Co0.1Mn0.1(OH)2Mole Than being 1.02:1, La (NO3)3·6H2O and Ni0.8Co0.1Mn0.1(OH)2The molar ratio of middle nickel ion is 1:79.
La-NCM811 prepared by embodiment 5 is assembled into CR2025 button cells as positive electrode and carries out electrochemistry Performance test.Constant current charge-discharge test, first Zhou Fang electricity are carried out under 2.75V~4.5V voltage ranges, 30 DEG C and 0.1C multiplying powers Capacity is 209.1mAh/g, and discharge capacity of the cycle after 30 weeks is 193.4mAh/g, capacity retention ratio 92.5%.In 2.75V Constant current charge-discharge test is carried out under~4.5V voltage ranges, 30 DEG C and 1C multiplying powers, first week discharge capacity is 193mAh/g, is recycled Discharge capacity after 500 weeks is 97.2mAh/g, capacity retention ratio 50.4%.
Embodiment 6
First by LiOHH2O add in mortar in, dry grind 15min after, then with Ni0.8Co0.1Mn0.1(OH)2And La (NO3)3·6H2Mixture after ultrasound, is then transferred in mortar, first dry grind 30min, adds by O ultrasound 1h in ethanol Ethyl alcohol simultaneously continues to grind 20min, then the mixture after wet-milling is placed in oxygen atmosphere, be first heated to 550 DEG C and keeps the temperature 4h, then It is warming up to 850 DEG C and keeps the temperature 18h, furnace cooling obtains surface layer doping La3+NCM tertiary cathode materials Li [Ni0.79Co0.1Mn0.1La0.01]O2, it is abbreviated as La-NCM811；Wherein, LiOHH2O and Ni0.8Co0.1Mn0.1(OH)2Mole Than being 0.98:1, La (NO3)3·6H2O and Ni0.8Co0.1Mn0.1(OH)2The molar ratio of middle nickel ion is 1:79.
La-NCM811 prepared by embodiment 6 is assembled into CR2025 button cells as positive electrode and carries out electrochemistry Performance test.Constant current charge-discharge test, first Zhou Fang electricity are carried out under 2.75V~4.5V voltage ranges, 30 DEG C and 0.1C multiplying powers Capacity is 207.2mAh/g, and discharge capacity of the cycle after 40 weeks is 189.8mAh/g, capacity retention ratio 91.6%.In 2.75V Constant current charge-discharge test is carried out under~4.5V voltage ranges, 30 DEG C and 1C multiplying powers, first week discharge capacity is 189.7mAh/g, is followed Discharge capacity of the ring after 500 weeks be 95.1mAh/g, capacity retention ratio 50.1%.
Comparative example 1
The preparation process of original tertiary cathode material NCM811 undoped with La is as follows：
(1) according to Mn:Ni:Co=8:1:Manganese sulfate, nickel sulfate and cobaltous sulfate are dissolved in deionized water by 1 molar ratio, Obtain the sulfate solution of 2mol/L；
(2) alkaline aqueous solution containing 2mol/L sodium carbonate and 2mol/L ammonium hydroxide is configured；
(3) prepared sulfate solution and alkaline aqueous solution are added continuously to peristaltic pump with blender respectively And in the reaction kettle of logical nitrogen, and the addition rate control pH value by adjusting sulfate solution or alkaline aqueous solution, make pH 11 are stabilized to, controlling reaction temperature is 55 DEG C, and mixing speed 650r/min, sample introduction speed is adjusted to 0.25mL/min；Sample introduction After completely, after keeping ageing 6h in a nitrogen atmosphere, obtained sediment is filtered, wash, is dried, is obtained Ni0.8Co0.1Mn0.1(OH)2；
(4) by Ni0.8Co0.1Mn0.1(OH)2With LiOH powders according to 1:1.05 molar ratio is mixed, in present mortar Dry grind 25min, adds ethyl alcohol and continues to grind 25min, then for the mixture of the two to be placed in oxygen atmosphere, is first heated to 450 DEG C and 6h is kept the temperature, then be warming up to 750 DEG C and keep the temperature 12h, furnace cooling obtains NCM tertiary cathode materials, is abbreviated as NCM811。
CR2025 button cells are assembled into using the NCM811 prepared by comparative example 1 as positive electrode, and are carried out corresponding Electrochemical property test, test result analysis detailed in Example 1.
It is by the test result of above-described embodiment and comparative example it is found that provided by the invention in NCM tertiary cathode materials Surface layer transition metal layer doping La3+Method, the high rate performance of NCM tertiary cathode materials and head Zhou Ku can be significantly improved Human relations efficiency is especially more preferably notable to the chemical property improvement under high voltage high magnification and raw materials used at low cost Honest and clean, asepsis environment-protecting, entire technological process is simple, efficient, environmental protection, and experiment condition is wide in range, reliability is high, has good industry should Use prospect.

Claims (2)

1. La is adulterated on a kind of surface layer3+NCM tertiary cathode materials preparation method, it is characterised in that：The doping La3+NCM The chemical formula of tertiary cathode material is Li [Ni0.8-xCo0.1Mn0.1Lax]O2, wherein 0.005≤x≤0.03；
The method step is as follows,
By nickel cobalt manganese hydroxide precursor powder, lanthanum nitrate powder and lithium hydroxide powder after mixing, then it is placed in oxygen Calcined under gas atmosphere, first at 450 DEG C~550 DEG C keep the temperature 4h~6h, then be warming up to 750 DEG C~850 DEG C and keep the temperature 12h~ 20h, furnace cooling obtain surface layer doping La3+NCM tertiary cathode materials；
Wherein, the mole ratio of the molal quantity of lithium hydroxide and nickel cobalt manganese hydroxide precursor powder is 0.98~1.05:1, The molar ratio of the molal quantity of lanthanum nitrate and nickel ion in nickel cobalt manganese hydroxide precursor powder is 1:(25.6~159).
2. a kind of surface layer doping La according to claim 13+NCM tertiary cathode materials preparation method, feature exists In：First by lithium hydroxide add in mortar in, dry grind 10min~15min, then with before lanthanum nitrate powder and nickel cobalt manganese hydroxide Body ultrasound 1h~2h, then the mixture after ultrasound is transferred in mortar in ethanol is driven, after the 20min~30min that first dry grinds, then Ethyl alcohol wet-milling 20min~30min is added in, then is placed under oxygen atmosphere and is calcined.
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